Polyurethane compositions



3,474,047 PQLYURETHANE COMPOSITIONS Paul E. Pelletier, lElmwood Park, and Floy Pelletier, lLoclrport, 111., assignors, by mesne assignments, to Wyandotte Chemicals Corporation, a corporation of Michigan No Drawing. Filed Aug. 28, 1959, Ser. No. 836,579 int. Cl. C08g 53/10, 51/58, 41/00 US. Cl. 2602.5 8 Claims ABSTRACT OF Tl-E DISCLOSURE Polyurethanes are rendered fire-retardant by using alkylene oxide adducts of phosphonic acids as an active hydrogen reactant.

The present invention relates to polyurethane compositions produced by reaction of polyisocyanates with hydroxy compounds produced by reaction of alkylene oxides with phosphonic acid. The invention includes mixtures of polyisocyanates with the alkylene oxide-phosphonic acid reaction products as well as the polyurethane resins possessing improved resistance to burning and flame propagation which may be produced therefrom. Outstanding results are obtained when the polyurethane resin-producing reaction takes place in the presence of Water or other blowing agent to produce polyurethane foams which are characterized by non-infiammability and the capacity to self-extinguish fires.

In accordance With the invention an alkylene oxide is reacted with a phosphorus-containing acid having the formula:

wherein R is a monovalent and R a divalent, aliphatic, cycloaliphatic, aromatic or heterocyclic radical which may be saturated or unsaturated and/or substituted with noninterfering substituents, such as halogen atoms, ether and ester radicals, and the like. Examples of such phosphonic acids are benzenephosphonic acid, cyclohexanephosphonic acid, propanephosphonic acid, methanediphosphonic acid, cyclohexenephosphonic acid, dichlorobutanephosphonic acid, butanediphosphonic acid, methoxymethanephosphonic acid, xylenephosphonic acid, 2- hexenephosphonic acid, tetradecanephosphonic acid, 3,5- dichlorodecauephosphonic acid, 2,3,4-trimethylpentanephosphonic acid, and chlorocyclohexanephosphonic acid. The phosphorus-containing acids referred to in the above formula are known as monophosphonic acids and diphosphonic acids. Particularly preferred Phosphorus-containing acids in accordance with the invention are benzenephosphonic acid, cyclohexanephosphonic acid, propanephosphonic acid and methanediphosphonic acid.

The alkylene oxides which may be used are preferably illustrated by ethylene oxide, propylene oxide, butylene oxide and styrene oxide. The preferred oxides contain the 1,2 epoxy group, but the invention is not so limited and 2,3 butylene oxide may be used. The invention includes epichlorohydrin and other halohydrins such as epiiodohydrin, epifiuorohydrin, epibromohydrin, etc., and higher molecular weight oxides such as octylene oxide as well as dioxides (diepoxides) illustrated by the diglycidyl ether nite States Patent monomer of bisphenol A. Halogenated alkylene oxides such as epichlorohydrin may also be used.

It is known as taught, for example, in United States Patent 2,372,244, to react phosphoric acid or phosphorus acid with olefin oxides to produce reaction products possessing primary hydroxyl groups as indicated by the reaction equations set forth in said patent.

The products of the invention are very different from those of Patent 2,372,244 since when sufficient propylene oxide is reacted with phosphoric acid or phosphorus acid (about 6 mols of oxide per mol of acid) to produce a neutral product sufficiently reactable with polyisocyanates for polyurethane foam production, the foam product is not self-extinguishing or non-inflammable. Using the phosphonic acids specified by the invention, reaction with alkylene oxides may be effected to provide at least substantially neutral products which are reactive with polyisocyanates to form non-inflammable and self-extinguishing polyurethane foams.

At least one epoxy equivalent of alkylene oxide is reacted with each hydroxyl equivalent of the phosphonic acid. Preferably, the reaction is continued further to provide an at least substantially neutral reaction product in which at least 1.5 epoxy groups are reacted per hydroxy equivalent in the starting phosphonic acid.

The reaction products of the invention are hydroxycontaining materials. These may be used alone for reaction with polyisocyanates or in admixture with other compounds reactive with polyisocyanates such as hydroxycontaining polyesters and polyethers. Whatever proportion of the reaction product of the invention is used in the mixture provides an improvement in fire resistance and it is preferred to use enough to provide self-extinguishing characteristics to the foam product. The self-extinguishing characteristic is determined in accordance with method D63556T of the- American Society for Testing Materials.

The reaction of alkylene oxides with phosphonic acids in accordance with the invention can be performed at various pressures, atmospheric and superatmospheric ressures, and the temperature of reaction can vary from 50 to 500 F. Low temperature operation, while possible, is inconvenient because the reaction is exothermic and proceeds more rapidly as the temperature is increased. T emperatures above 220 F., though useful, are less desirable because the products tend to darken. Preferred reaction temperature is within the range of 10O180 F. providing an easily controlled reaction without darkening of the product.

The reaction is preferably effected by incremental addition of the alkylene oxide to the phosphonic acid, though this is not essential. Desirably, the phosphonic acid is maintained at a temperature of l20 F. by cooling while the alkylene oxide is added. This prevents local over-heating and excessive reaction temperature which may result from the exothermic reaction. After the alkylene oxide addition has been completed and the reactants intimately mixed together by stirring, the temperature is desirably raised slowly to the preferred reaction temperature and held at this temperature until the reaction has been completed. Completion of the reaction may be determined by the substantial exhaustion of alkylene oxide from the reaction mixture or, conveniently, by the achievement of a substantially neutral pH. Any slight excess of alkylene oxide which may be present at the completion of the reaction can be removed by heat under vacuum.

The invention is illustrated in the following examples:

propylene oxide is added with stirring until sufiicient propylene oxide is present to provide a slurry. A strong exothermic reaction occurs and the flask is cooled to maintain a temperature of from 90120 F. When the exotherm subsides a liquid product is formed and propylene oxide is added slowly and continuously to the reaction liquid until exothermic activity ceases. The temperature is then raised slowly to l30-140 F. and held at this temperature for 1 hour under reflux. The product at this point is essentially neutral upon titration and contains a slight excess of propylene oxide which is removed by application of vacuum while maintaining a temperature of 130- 140 F.

The final yield is 470 grams corresponding to the reaction of 270 grams of propylene oxide and providing a product in which the ratio of reacted epoxy group to hydroxyl radical in the initial phosphonic acid is about 1.8-1.9: 1. The product has an actual hydroxyl number by acetylation method of 293, acidity of 0, and a viscosity of 1020 centipoises measured at 77 -F.

EXAMPLE II A typical foaming composition was prepared using the hydroxy compound obtained in Example I as follows:

Quasi prepolymer composition 32.0 partsI-Iydroxy compound of Example I.

68.0 partsToluene diisocyanate (80/20 mixture of the 2,4 and 2,6 isomers).

(Mixed and allowed to exotherm to 180 F. while stirring for 30 minutes, hold at 180 F. for 40 minutes and then allow to cool to room temperature. Analyzed NCO 23.1%

Foaming mixture (blowing The composition set forth above foams to produce a very fine celled foam product having excellent tensile strength and load bearing qualities. It is self-extinguishing according to ASTM Method D635-56T.

It will be observed that the foaming composition of Example 11 includes a proportion of a polyester which functions to improve the physical properties of the foam product. Various polyesters or polyethers may be used having an hydroxyl number in the range of 250 to 700 in order to improve the physical properties of the foam product.

Polyesters of polycarboxylic acids with polyols such as glycols are preferred, the glycol reactant being used in excess to provide hydroxyl functionality in the desired range. Polyethers may also be used such as high molecular weight epoxy resins in which the repeating unit contains secondary hydroxyl groups. Similarly, esters of these epoxy resins in which the epoxy groups are reacted but the hydroxyl groups are unreacted are also suitable.

From 15 to 60 parts of the polyester or polyether component is desirably used for every 85 to 40 parts of the hydroxy compounds of the invention which are present in the foaming mixture. These polyesters or polyethers preferably possess a hydroxyl number of from 450 to 480.

It will be appreciated that the polyester component can be omitted from Example II while still providing selfextinguishing foams although the foam products possess less desirable tensile strength and load bearing properties.

It will be understood that the production of the polyurethane foam may be accomplished in various ways known to the art, the foam production illustrated in Examples I and II being simply illustrative. In this regard, reference is made to the text entitled Polyurethanes by 4 Bernard A. Dombrow, published by Reinhold Publishing Corporation, 1957, where reference is made to various techniques for the production of polyurethane foams, including the one-shot procedure as well as various procedures including polyurethane prepolymers.

The following is a further example of a method of forming a hydroxy compound in accordance with the invention which may be reacted with a polyisocyanate as in Example II to produce a self-distinguishing polyurethane composition as herein described.

EXAMPLE III A two liter, three neck flask was fitted with a reflux condenser, stirring motor, thermometer, and addition tube connected to a separatory funnel for continuous addition of epichlorohydrin.

1060 gms. or 11.5 moles of epichlorohydrin were added continuously to 450 gms. or 2.85 moles of benzene phosphonic acid at a temperature of -200" F. Water cooling was employed primarily at the initial stages of the reaction.

After all of the epichlorohydrin was added, the product was held at 200 F. for two hours, at which time it titrated neutral. The product was then vacuum distilled at 200 F. to remove any excess, unreacted epichlorohydrin.

The yield was 1495 gms. and indicates that nearly 4 moles of epichlorohydrin were added to 1 mole of benzene phosphonic acid.

The final product is a clear, slightly wine colored liquid which has a pH of 5 and is essentially neutral on methyl alcohol, and has a hydroxyl number of 218. Similar products having a pH ranging from 2 to 6 are useful in accordance with the invention.

In a foam producing mixture in accordance with the invention, the stated presence of a polyisocyanate component is intended to include the polyisocyanate compound per se, such as toluene diisocyanate, or a reaction product of the polyisocyanate which liberates free polyisocyanate when heated, such as a compound with phenol, or a quasi prepolymer of the monmeric polyisocyanate which provides isocyanate polyfunctionality, such as the prepolymers illustrated in the present examples.

Any polyisocyanate will react with the hydroxy compounds of the invention such as toluene diisocyanate (pure or mixed isomers), hexamethylene diisocyanate, 1,5 naphthalene diisocyanate, methylene bis-4-phenyl isocyanate, etc., however the preferred isocyanates are the various commercial toluene diisocyanates because of their availability and desirable physical properties which are well understood by the art.

As is conventional, the foaming composition includes a blowing agent. This term includes various types of materials which are known to possess an expanding function. Thus, water reacts with isocyanate to produce carbon dioxide gas thereby providing a blowing agent which enters into the polymerization reaction providing an internal blowing agent. External blowing agents which expand or decompose to yield gaseous products, normally upon increase in temperature, may also be used. These are termed external agents because they do not enter into the isocyanate polymerization reaction. External blowing agents are illustrated by the materials generally known as freons which are lower molecular weight hydrocarbons usually containing both fluorine and chlorine substituents. Other external blowing agents are illustrated by sodium and ammonium bicarbonate, etc.

As is generally accepted in the urethane art when preparing a foam the equivalents of isocyanate are preferably approximately equal to the equivalents of hydroxyls (or other radicals providing active hydrogen) designed to react with the polyisocyanate to produce the urethane polymer. The ratio of isocyanate to hydroxyl can vary considerably in accordance with the invention in the same manner as is known for the conventional hydroxyl-containing materials known to the art.

The invention is defined in the claims which follow.

We claim:

A fire-retardant polyurethane resin comprising the reaction product of an organic polyisocyanate and an at least substantially neutral hydroxy reaction product of an oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide with a phosphonic acid, said hydroxy reaction product containing at least 1.5 reacted epoxy groups per hydroxy equivalent of said acid.

2. The fire-retardant polyurethane resin of claim 1 in which said phosphonic acid is a monophosphonic acid.

3. The fire-retardant polyurethane resin of claim 1 in which said at least substantially neutral reaction product contains from 1.81.9 reacted epoxy groups per hydroxyl equivalent of said acid.

4. The fire-retardant polyurethane resin or" claim 3 in which said organic polyisocyanate comprises tolylene diisocyanate and said diisocyanate and said at least substantially neutral reaction product are present in approximately equivalent amounts.

5. The fire-retardant polyurethane resin of claim 1 in the form of a foam.

6. A process of producing a fire-retardant polyurethane foam consisting of co-reacting a mixture comprising an organic polyisocyanate, a blowing agent, and an at least substantially neutral hydroxy reaction product of an oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide with a phosphonic acid, said hydroxy reaction product containing at least 1.5 reacted epoxy groups per hydroxy equivalent of said acid.

7. A fire-retardant polyurethane resin comprising the reaction product of (A) an organic polyisocyanate and (B) the reaction product consisting of the reaction of a phosphonic acid with an oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide.

8. A fire-retardant polyurethane resin comprising the reaction product of an organic polyisocyanate and the reaction product of an oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide with a phosphonic acid, said lastnamed reaction product containing at least one reacted epoxy equivalent of said oxide per hydroxyl equivalent of said phosphonic acid.

References Cited UNITED STATES PATENTS 2,732,367 1/1956 Shrka 260-77.5 2,764,565 9/1956 Hoppe 64 al. 260-2.5 2,856,369 10/1958 Smith 61; a1 260-2 2,906,642 9/1959 Dennis 2602.5

HOSEA E. TAYLOR, 111., Primary Examiner M. B. FEIN, Assistant Examiner US. Cl. X.R. 

